Electric double layer capacitor

ABSTRACT

A solution or dispersion of an ion-permeable compound, a carbon fine particle a, and a solvent is coated on a conductive sheet such as an aluminum foil, the coat is dried to form a film a. which allows to obtain a collector for an electric double layer capacitor. A solution or dispersion of a binder, a carbon fine particle b, an activated carbon b, and a solvent is coated on the film a, the coat is dried to form a film b, which results in obtaining an electrode for an electric double layer capacitor. The electrode is piled on a separator, and immersed in an electrolytic solution to obtain an electric double layer capacitor.

ELECTRIC DOUBLE LAYER CAPACITOR

This application claims benefit pursuant to 35 U.S.C. §119(e)(1) ofProvisional Application No. 60/727,548 filed on Oct. 18, 2005, thedisclosures of which are incorporated herein by reference. Thisapplication is based on Japanese Patent Application No.. 2005-296444filed on Oct. 11, 2005, and Japanese Patent Application No. 2006-216299filed on Aug. 8, 2006, the contents of which are incorporated herein byreference.

TECHNICAL FIELD

The invention relates to a collector for an electric double layercapacitor, an electrode for an electric double layer capacitor, and anelectric double layer capacitor, and a method of manufacturing the same.

Background Art

An electric double layer capacitor is quickly chargable anddischargable, tough against over-charge&discharge, long in life forcause of no chemical reaction, workable under wide range of temperature,and easy on the environment for cause of heavy metal free, and has otherproperty which battery does not have. An electric double layer capacitoris mainly employed for a memory backup power supply and so on. Anelectric double layer capacitor is researched in application to electricpower storing system or engine assist for hybrid car by assembling withbattery such as solar battery and fuel cell.

An electric double layer capacitor comprises a pair of polarizableelectrodes comprising a laminate of a collector such as an aluminum foiland a composition containing an activated carbon, in which the pair ofpolarizable electrodes set facing each other in solution containingelectrolytic ion, and a separator is interposed between the polarizableelectrodes. Impressing of direct current voltage into the electrodescauses drawing anion in solution to cathode (positive electrode) anddrawing cation in solution to anode (negative electrode), making anelectric double layer at the interface between electrode and solution.And the electric double layer can supply electric energy.

An internal resistance of an electric double layer capacitor needs to beas low as possible in order to obtain an electric double layer capacitorhaving high output and high capacity. It is known that an internalresistance of a capacitor is caused from an electrolytic solution, apolarizable electrode, a collector, and interface between them.

So attempt to lower an internal resistance of the capacitor by loweringa volume resistance of the collector or the electrode has been carriedout.

Patent document 1 discloses an electrode for an electric double layercapacitor comprising a laminate of an aluminum foil having a thicknessof 10 to 50 μm, a conductive layer having a thickness of 0.2 to 20 μmand an electrode layer having a thickness of 80 to 500 μm in turn. Theconductive layer is made from a conductive coating material comprising agraphite powder as a conductive material and polyamide-imide resin as abinder.

[Patent Document 1] JP-2002-270470-A

Patent document 2 discloses an electrode for an electric double layercapacitor comprising a laminate of an electrode layer containing acarbon material having a specific surface area of 100 to 2500 m²/g and ahigh conductive layer which is porous and has an electric conductivityhigher than that of the above electrode layer in turn, in which theelectrode layer is on a collector for an electrode. There is describedthat the electrode layer containing a carbon material having a specificsurface area of 100 to 2500 m²/g is pasted on the collector for anelectrode by using a conductive adhesive containing carbon.

[Patent Document 2] JP-2003-309045-A

Patent document 3 discloses a collector for an electric double layercapacitor comprising: a film comprising a conductive material andthermoplastic resin, and a low electric resistance layer being on thefilm

[Patent Document 3] JP-2004-31468-A

DISCLOSURE OF THE INVENTION

Subject to be Solved by the Invention

Conventional electric double layer capacitor including those in theabove patent documents, however, is relatively large in an internalimpedance, and is unsatisfactory for a quick charge-discharge.

In view of the matter, the invention is aimed at producing a collectorfor an electric double layer capacitor, an electrode for an electricdouble layer capacitor, and a method of manufacturing the same, for anelectric double layer capacitor having low impedance and high capacity,and being quickly chargable and dischargable by high electric current.

Means for Solving the Subject

After the inventor did every research to achieve the goal, it was foundout that use of an ion-permeable compound instead of conventionalcompound for binder, specifically forming of a film having both ofion-permeability and electric conductivity, more specifically forming ofa film a comprising ion-permeable compound and carbon fine particle a ona conventional collector (Aluminum foil etc.) for an electric doublelayer capacitor can result in obtaining an electric double layercapacitor having low impedance and high capacity, and being quicklychargable and dischargable. The invention was made by furtherresearching on the found out knowledge.

The invention provides the following means for solving.

-   (1) A collector for an electric double layer capacitor comprising;

a conductive sheet, and

a film a comprising an ion-permeable compound and a carbon fine particlea, in which the film a is on the conductive sheet.

-   (2) The collector for an electric double layer capacitor according    to (1), in which the conductive sheet is aluminum foil, etching-foil    of aluminum or punching-foil of aluminum.-   (3) The collector for an electric double layer capacitor according    to (1) or (2), in which the ion-permeable compound is a compound not    being swellable with an organic solvent.-   (4) The collector for an electric double layer capacitor according    to any one of (1) to (3), in which the ion-permeable compound is a    compound which does not come off in a friction peeling test with    organic solvent.-   (5) The collector for an electric double layer capacitor according    to any one of (1) to (4), in which the ion-permeable compound is    1×10⁻² S/cm or more in a permeability of fluoride ion.-   (6) The collector for an electric double layer capacitor according    to any one of (1) to (5), in which the ion-permeable compound is    50,000 or less in an average molecular weight.

(7) The collector for an electric double layer capacitor according toany one of (1) to (6), in which the ion-permeable compound ispolysaccharides or cross-linked polysaccharides.

-   (8) The collector for an electric double layer capacitor according    to any one of (1) to (6), in which the ion-permeable compound is    polysaccharides cross-linked by any of acrylamide, acrylonitrile,    chitosan pyrrolidone carboxylate, hydroxypropyl-chitosan, phthalic    anhydride, maleic anhydride, trimellitic anhydride, pyromellitic    anhydride, and acid anhydride..-   (9) The collector for an electric double layer capacitor according    to (7) or (8), in which the polysaccharides is chitosan or chitin.-   (10) The collector for an electric double layer capacitor according    to any one of (1) to (9), in which the film a does not come off in a    tape peeling test (JIS D0202-1988).-   (11) The collector for an electric double layer capacitor according    to any one of (1) to (10), in which the film a is obtained by    heat-curing.-   (12) The collector for an electric double layer capacitor according    to any one of (1) to (11), in which the film a further comprises    activated carbon a.-   (13) The collector for an electric double layer capacitor according    to any one of (1) to (12), in which the carbon fine particle a is    acicular or cylindric shape.-   (14) An electrode for an electric double layer capacitor comprising:

a collector for an electric double layer capacitor according to any oneof (1) to (13), and

a film b comprising a binder, a carbon fine particle b, and an activatedcarbon b, in which the film b is on the film a in the collector.

-   (15) The electrode for an electric double layer capacitor according    to (14), in which the carbon fine particle b is acicular or    cylindric shape.-   (16) The electrode for an electric double layer capacitor according    to (14) or (15), in which the activated carbon b is 800 to 2500 m²/g    in a BET specific surface area.-   (17) The electrode for an electric double layer capacitor according    to any one of (14) to (16), in which the binder comprises an    ion-permeable compound.-   (18) A method of producing a collector for an electric double layer    capacitor comprising steps of:

coating a solution or dispersion of an ion-permeable compound, a carbonfine particle a and a solvent on to a conductive sheet, and

drying the coat to form a film a.

-   (19) The method of producing a collector for an electric double    layer capacitor according to (18), in which the ion-permeable    compound is 1×10⁻² S/cm or more in a permeability of fluorinde ion.-   (20) The method of producing a collector for an electric double    layer capacitor according to (18) or-   (19), in which the ion-permeable compound is 50,000 or less in an    average molecular weight.-   (21) The method of producing a collector for an electric double    layer capacitor according to any one of (18) to (20), in which the    ion-permeable compound is polysaccharides or cross-linked    polysaccharides.-   (22) The method of producing a collector for an electric double    layer capacitor according to any one of (18) to (20), in which the    ion-permeable compound is polysaccharides cross-linked by any of    acrylamide, acrylonitrile, chitosan pyrrolidone carboxylate,    hydroxypropylchitosan, phthalic anhydride, maleic anhydride,    trimellitic anhydride, pyromellitic anhydride, and acid anhydride.-   (23) The method of producing a collector for an electric double    layer capacitor according to any one of (18) to (22), in which the    carbon fine particle a is acicular or cylindric shape.-   (24) The method of producing an electrode for an electric double    layer capacitor comprising steps of:

coating a solution or dispersion of a binder, a carbon fine particle b,an activated carbon b, and a solvent on to the film a in the collectorfor an electric double layer capacitor according to any one of (1) to(13), and

drying the coat to form a film b.

-   (25) The method of producing an electrode for an electric double    layer capacitor comprising steps of:

coating a solution or dispersion of an ion-permeable compound, a carbonfine particle a and a solvent on to a conductive sheet,

drying the coat to form a film a

coating a solution or dispersion of a binder, a carbon fine particle b,an activated carbon b, and a solvent on to the film a, and

drying the coat to form a film b.

-   (26) The method of producing an electrode for an electric double    layer capacitor according to (25), in which the ion-permeable    compound is 1×10⁻² S/cm or more in a permeability of fluoride ion.-   (27) The method of producing an electrode for an electric double    layer capacitor according to (25) or-   (26), in which the ion-permeable compound is 50,000 or less in an    average molecular weight.-   (28), The method of producing an electrode for an electric double    layer capacitor according to any one of (25) to (27), in which the    ion-permeable compound is polysaccharides or cross-linked    polysaccharides.-   (29) The method of producing an electrode for an electric double    layer capacitor according to any one of (25) to (28), in which the    ion-permeable compound is polysaccharides cross-linked by any of    acrylamide, acrylonitrile, chitosan pyrrolidone carboxylate,    hydroxypropylchitosan, phthalic anhydride, maleic anhydride,    trimellitic anhydride, pyromellitic anhydride, and acid anhydride.-   (30) The method of producing an electrode for an electric double    layer capacitor according to any one of (25) to (29), in which the    carbon fine particle a is acicular or cylindric shape.-   (31) The method of producing an electrode for an electric double    layer capacitor according to any one of (24) to (30), in which the    carbon fine particle b is acicular or cylindric shape.-   (32) The method of producing an electrode for an electric double    layer capacitor according to any one of (24) to (31), in which the    activated carbon b is 800 to 2500 m²/g in a BET specific surface    area.-   (33) An electric double layer capacitor comprising:

electrode for an electric double layer capacitor according to any one of(14) to (17), separator, and an electrolytic solution.

-   (34) The electric double layer capacitor according to (33) which is    laminate type capacitor or reel type capacitor.-   (35) A method or producing an electric double layer capacitor    comprising steps of:

piling the electrode for an electric double layer capacitor according toany one of (14) to (17) and separator, and immersing the pile of theelectrode and the separator in an electrolytic solution.

(36) A power supply system comprising the electric double layercapacitor according to (33) or (34).

-   (37) A vehicle in which the electric double layer capacitor    according to (33) or (34) is employed.-   (38) A railroad in which the electric double layer capacitor    according to (33) or (34) is employed.-   (39) A ship in which the electric double layer capacitor according    to (33) or (34) is employed.-   (40) An aircraft in which the electric double layer capacitor    according to (33) or (34) is employed.-   (41) A portable apparatus in which the electric double layer    capacitor according to (33) or (34) is employed.-   (42) An apparatus for office work in which the electric double layer    capacitor according to (33) or (34) is employed.-   (43) A solar power generation system in which the electric double    layer capacitor according to (33) or (34) is employed.-   (44) A wind power generation system in which the electric double:    layer capacitor according to (33) or (34) is employed.-   (45) A communication apparatus in which the electric double layer    capacitor according to (33) or (34) is employed.-   (46) An electronic tag in which the electric double layer capacitor    according to (33) or (34) is employed.

In the description, “

” and “

” in Japanese include a boundary value x and y respectively. “

” and “

” in Japanese don't include a boundary value x and y respectively. Arange of “x˜x y” in Japanese includes boundary value x and y.

EFFECTS OF THE INVENTION

In the invention, a collector for an electric double layer capacitor, anelectric double layer capacitor employing an electrode for an electricdouble layer capacitor which an electrode layer (film b) is applied to:the collector can have low impedance and high capacity, and is quicklychargable and dischargable by high electric current.

The collector for an electric double layer capacitor, the electrode foran electric double layer capacitor and the electric double layercapacitor can be easily obtained by the method of producing in theinvention.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 11 schematic illustration of sectional formation of the collectorfor an electric double layer capacitor obtained in Example 1.

schematic illustration of sectional formation of the electrode for anelectric double layer capacitor obtained in Example 2.

illustration of glass cell for measurement of fluoride ion permeability.

EXPLANATION OF SYMBOL

1: Aluminum foil

2: film a

3: carbon fine particle

4: ion-permeable compound

5: activated carbon b

6: film b (polarizable electrode layer)

7: binder

BEST MODE FOR CARRYING OUT THE INVENTION

A collector for an electric double layer capacitor of a: preferable modein the invention comprises a conductive sheet and film a comprising anion-permeable compound and carbon fine particle a in which the film a ison the sheet.

The conductive sheet comprised in the collector for an electric doublelayer capacitor of a preferable mode in the invention includes not onlya foil having no hole, but also a foil having hole such as apunching-metal foil and a lattice foil. The conductive sheet is notparticularly limited as long as it is made of conductive material, aconductive metal sheet and a conductive resin sheet are mentioned. Analuminum sheet and aluminum alloy sheet may be specifically preferablymentioned. Used as aluminum foil is usually a foil such as A1085, A3003in JIS (Japanese Industrial Standards).

Though the conductive sheet may be smooth, the favorable sheet is asheet (etching foil) roughened by an electrical etching, a chemicaletching or so on.

The conductive sheet is not particularly limited, usually 5 μm to 100 μmin a thickness.

Thickness is so thin that mechanical strength is insufficient and it iseasy to tear the conductive sheet. Thickness is so thick that theconductive sheet largely wastes the volume in the electric double layercapacitor, and an electric capacity per volume of the capacitor is aptto be lowered.

A film a comprised in the collector of a preferable mode in theinvention comprises a carbon fine particle a and an ion-permeablecompound.

The carbon fine particle a used in the invention is conductive fineparticle containing carbon as main constituent. Acetylene black, ketjenblack, vapor grown carbon fiber, graphite (black lead) and so on arefavorable for the carbon fine particle a.

The carbon fine particle a is preferably 1×10⁻¹ Ω·cm or less in aelectric resistance of a powder compact of 100%. The carbon fineparticle a may be used alone or in combination with at least two.

The carbon fine particle a is not particularly limited by a particlesize, is preferably 10 nm to 50 μm, more preferably 10 nm to 100 nm in avolume average particle size.

The carbon fine particle a may be spherical shape, preferably acicularor cylindric shape (anisotropic shape). Anisotropic carbon fine particlea is large in a surface area per weight, which allows to increase acontact area with a conductive sheet, the following activated carbon band so on, so electric conductivity between an aluminum foil and theactivated carbon b can be enlarged by even a little carbon fine particlea. Mentioned as anisotropic carbon fine particle a is a carbon nano-tubeor a carbon nano-fiber. The carbon nano-tube or the carbon nano-fiberhaving a fiber diameter of usually 0.001 to 0.5 μm, preferably 0.003 to0.2 μm; and a fiber length of usually 1 to 100 μm, preferably 1 to 30 μmis favorable for increasing a conductivity. Conductive fine particlessuch as metallic carbide and metallic nitride may be used together withthe carbon fine particle a.

The ion-permeable compound used in tho invention is not particularlylimited as long as it has ion-permeable property.

The ion-permeable compound having a large ion-permeability ispreferable. Specifically the ion-permeable compound having a fluorideion permeability of 1×10⁻² S/cm or more is favorable. A fluoride ionpermeability can be determined as the following. Ion-permeable compoundis dissolved in water or n-methylpyrrolidone to adjust viscosity, isapplied on a substrate and is dried for 5 minutes at 150° C. in anatmosphere of air to obtain a thin film (ion-permeable film). The thinfilm is peeled off the substrate for measuring a thickness d [μm]. Asshown in FIG. 3, 212 cm³ of pure water having temperature of 25° C. andan electric conductivity σ₀ [S/cm] are filled into a glass cell having acaliber of 6 cm and a depth of 7.5 cm, and the glass cell is sealed withthe above thin film. On to the above thin film, 3.18 cm³ (diameter: 4.5cm, height: 2 mm) of a solution of hydrogen fluoride having temperatureof 25° C. and concentration of 0.005% by mass are contacted at 15.9 cm²in a contact area for 60 seconds. The thin film is taken off the glasscell, and an electric conductivity σ₁ [S/cm] of the pure water in thecell is measured. An ion-permeability T [S/cm] is calculated by thefollowing formula with the electric conductivity σ₀ of the pure water atsealing and the electric conductivity al of the pure water aftercontacting with the solution of hydrogen fluoride.T=(σ₁−σ₀)×d/0.1

Also, the ion-permeable compound is preferably 50,000 or less in anumber average molecular weight.

The ion-permeable compound used in the invention is preferably acompound not being swellable with an organic solvent. Also theion-permeable compound is preferably a compound which does not come offin a friction peeling test with an organic solvent. It is preferablethat the film does not swell or dissolve in the electrolytic solution,since an organic solvent may be used for an electrolytic solution of anelectric double layer capacitor.

Swellability with an organic solvent is estimated by whether film of anion-permeable compound swells: or not after the film is immersed in theorganic solvent (30° C.) used for an electrolytic solution for 60minutes.

In a friction peeling test with organic solvent, the surface of the filmof an ion-permeable compound is rubbed with a cloth penetrated withorganic solvent 10 times at 100 g in load, and then the film is observedwhether the film peels or not.

Polysaccharides or cross-linked polysaccharides are mentioned as thefavorable ion-permeable compound.

Polysacchairides is a high molecular compound which many monosaccharides(including monosaccharide substitution products or monosaccharidederivatives) are polymerized with glycoside bond. Polysaccharidesresolves into many monosaccharides by hydrolysis. Polysaccharides isusually described as polymer of 10 or more of monosaccharides. Thepolysaccharides may have substituent, and include polysaccharides (aminosugars) which amino group is substituted for alcoholic hydroxyl group,substitution products with carboxyl group or alkyl group, de-acetylationproducts of polysaccharides and the like. Polysaccharides may be any ofhomopolysaccharides and heteropolysaccharides.

Mentioned as polysaccharides are agarose, amylose, amylopectin, araban,arabinan, arabino-galactan, alginic acid, inulin, carrageenan,galactans, galactosamine (chondrosamine), glucan, xylan, xyloglucan,carboxyalkylchitin, chitin, glycogen, glucomannan, keratan sulfate,colominic acid, chondroitin sulfate A, chondroitin sulfate B,chondroitin sulfate C, cellulose, dextran, starch, hyaluronic acid,fructan, pectinic acid, pectinic substance, heparanic acid, heparin,hemicellulose, pentosan, β-1,4′-mannan, α-1,6′-mannan, lichenin, levan,lentinan, chitosan and the like. In these, chitin, chitosan arepreferable.

As Crosslinker used for cross-linking poly-saccharides, any ofacrylamide, acrylo-nitrile, chitosan-pyrrolidone-carboxylate,hydroxy-propyl-chitosan, phthalic anhydride, maleic anhydride,trimcllitic anhydride, pyromellitic anhydride, and acid anhydride arefavorable.

More specifically, as ion-permeable compound are mentioned cross-linkedpolymer of cellulose by acrylamide, cross-linked polymer of cellulose bychitosan-pyrrolidone-carboxylate, chitosan or chitin cross-linked by thecrosslinkers, polysaccharides cross-linked by acryl based additives oracid anhydride and the like. The ion-permeable compound may be usedalone or in combination with at least two.

In the film a, ratio by mass of the ion-permeable compound and thecarbon fine particle a (=ion-permeable compound/carbon fine particle a)is preferably 20/80 to 99/1, more preferably 40/60 to 90/10.

The film a may comprise an activated carbon a if necessary. Theactivated carbon a comprised in the film a enlarges an electric capacityof an electric double layer capacitor. The activated carbon a may beselected from the mentioned as the following activated carbon b.

The film a is not particularly limited by the method of forming. Forexample, the ion-permeable compound, the carbon fine particle a, andoptionally the activated carbon a are dispersed or dissolved in solventto prepare composition, the composition can be applied on to aconductive sheet, and dried to form a film a.

Casting process, bar coating process, dipping process, printing processand the like are mentioned as the manner for applying. In these manners,bar coating process, casting process are favorable in view of easilycontrolling a thickness of film.

Solvent used in the composition is not particularly limited as long asit can disperse or dissolve the ion-permeable compound and the carbonfine particle a. Solvent is preferably added so as to be 10% by mass to100% by mass in solid content of the composition in order to adjust aviscosity of the composition. Almost 100% of solvent are removed bydrying after the application.

After drying, the film a is preferably heat-cured. The ion-permeablecompound comprising polysaccharides or crosslinked polysaccharidescontains curable material by heating. The above cross-linker may befurther added into the composition in order to harden the film a.

Thickness of the film a is preferably not less than 0.01 μm and not morethan 50 μm, more preferably not less than 0.1 μm, and not more than 10μm. The thickness is so thin that it is not apt to obtain the desiredeffect such as a decline of internal resistance. The thickness is sothick that the film a largely wastes the volume in the electric doublelayer capacitor, and an electric capacity per volume of the capacitor isapt to be lowered.

It is preferable that the film a adheres to the conductive sheet not topeel off, specifically the film a does not come off in a tape peelingtest (JIS D0202-1988).

Electrode for Electric Double Layer Capacitor

An electrode for an electric double layer capacitor of a preferable modein the invention comprises the above collector for an electric doublelayer capacitor, and a film b comprising a binder, a carbon fineparticle b, and an activated carbon b, in which the film b is on thefilm a in the collector.

The film b comprised in the electrode for an electric double layercapacitor of a preferable mode in the invention comprises a binder, acarbon fine particle b, and an activated carbon b.

The binder is known binder used in an electrode for an electric doublelayer capacitor. Mentioned as the binder are poly-vinyliden fluoride,poly-tetra-fluoro-ethylene, styrene-butadiene rubber and the like. Theliquid binder is favorable for mixing with the following activatedcarbon b and so on, in which the liquid binder is dispersion or solutionof binder in a solvent such as N-methylpyrrolidone, xylene, and water.The film b may contains the above ion-permeable compound.

The activated carbon b is preferably large in a specific surface area inview of enlarging an electric capacity. Specifically, the activatedcarbon b has a BET specific surface area of preferably 800 to 2500 m²/g.The activated carbon b is preferably 1 μm to 50 μm in an averageparticle size (D50). An average particle size (D50) of an activatedcarbon is a cumulative particle size at 50% measured by a microtracparticle size distribution measure.

The activated carbon b may employ the known activated carbon. Forinstance, coconut shell activated carbon, fibrous activated carbon andthe like are mentioned. The activated carbon is not particularly limitedby the method of activation, and the activated carbon obtained by asteam activation process, a chemical activation process and so on may beemployed. Activated carbon obtained by alkali activation process (alkaliactivated carbon) is favorable for obtaining a capacitor having highcapacity. The alkali activated carbon may be obtained by heating coconutshell, coke, char of polymer, hard-graphitizable coke, oreasy-graphitizable coke in the presence of alkali metallic compound. Aseasy-graphitizable coke, for instance, coke obtained by heating pitchsuch as petroleum based pitch, coal based pitch, or organic solventdissoluble constituent thereof; coke of polyvinyl-chloride compound areemployed. Mentioned as alkali metallic compound are sodium hydroxide,potassium hydroxide, potassium carbonate and the like.

The activated carbon b used in the invention is preferably 0.3 g/cm³ to0.9 g/cm³ in a harden bulk density (tapping density). A harden bulkdensity is so little that packing density is decreased and electriccapacity per volume or per cell of an electric double layer capacitor isapt to be lowered. A harden bulk density is so large that electriccapacity per weight is decreased, and the holding volume of electrolyticsolution is likely to be decreased, which results in being to fall aretention rate of capacity.

Ratio by mass of the binder and the activated carbon b(=binder/activated carbon b) in the film b is preferably 50/50 to 1/99,more preferably 30/70 to 3/97.

The carbon fine particle b is the same as the exampled as the abovecarbon fine particle a. Specifically, acetylene black, ketjen black,vapor grown carbon fiber, graphite (black lead) and so on may beemployed as the carbon fine particle b. In the film b are preferablycontained 2 to 10% by mass of the carbon fine particle b.

Thickness of the film b can be adjusted in accordance with the desiredelectric capacity, is preferably not less than 10 μm and not more than500 μm.

The film b is not particularly limited by the method of forming. Forexample, the binder, the carbon fine particle b, and the activatedcarbon b are dispersed or dissolved in solvent to prepare composition,the composition can be applied on the film a, and dried to form a filmb.

Casting process, bar coating process, dipping process, printing processand the like are mentioned as the manner for applying. In these manners,bar coating process, casting process are favorable in view of easilycontrolling a thickness of film.

Solvent used in the composition is not particularly limited as long asit can disperse or dissolve the binder, the carbon fine particle b andthe activated carbon b. Proper amount of solvent is preferably added inorder to adjust a viscosity of composition. Almost 100% of solvent areremoved by drying after the application.

An electric double layer capacitor of a preferable mode in the inventioncomprises the above electrode for an electric double layer capacitor,separator which is piled on the electrode, and an electrolytic solutionwhich the electrode and the separator are immersed in.

Any of non-aqueous electrolytic solution and aqueous electrolyticsolution known in the prior art may be employed as the electrolyticsolution in the electric double layer capacitor. Also high-molecularsolid electrolyte being non-aqueous electrolyte, polymer gelelectrolyte, and ionic liquid may be further employed as the otherelectrolyte.

As the aqueous electrolytic solution are mentioned sulfuric acid aqueoussolution, sodium sulfate aqueous solution, sodium hydroxide aqueoussolution and the like.

As non-aqueous electrolytic solution is mentioned an electrolyticsolution comprising: quarternary ammonium salts or quarternaryphosphonium salts used as electrolyte comprising cation represented byR¹R²R³R⁴N⁺ or R¹R²R³R⁴P⁺ (R¹, R², R³ and R⁴ are respectively alkyl grouphaving 1 to 10 of carbon atom, or allyl group), and anion such as BF₄ ⁻,PF₆ ⁻, and ClO₄ ⁻, and non-aqueous carbonate solvent such as ethylenecarbonate, and propylene carbonate used as solvent. The electrolyte andthe solvent may be respectively used alone or in combination with two ormore.

The separator piled on the electrode may be ionic permeable porousseparator. For example, micro-porous polyethylene film, micro-porouspolypropylene film, polyethylene non-woven fabric, polypropylenenon-woven fabric, non-woven fabric mixed with glass fiber, and the likemay be preferably used.

The electric double layer capacitor in the invention may be any of cointype capacitor which a pair of electrode sheets in the state that aseparator is interposed between the electrode sheets is put in ametallic case with electrolytic solution, reel type capacitor which apair of electrodes in the state that a separator is interposed betweenthe electrodes is rolled up, laminate type capacitor which a lot ofelectrodes in the state that a separator is respectively interposedbetween the electrodes are piled, and the like.

The electric double layer capacitor of a preferable mode in theinvention can be applied to power supply system. The electric doublelayer capacitor in the invention can be applied to a power supply systemfor car such as automobile and railroad; a power supply system for ship;a power supply system for aircraft; a power supply system for mobileelectronic equipment such as cellular phone, mobile informationterminal., and mobile electronic calculator; a power supply system foroffice work; a power supply system for a power generation system such assolar battery power generation system, wind power generation system andfuel cell system; a communication apparatus, and an electronic tag andthe like.

EXAMPLES

The following examples and comparative examples are shown to explain theinvention in the concrete.

The invention is not limited by the following examples.

Example 1

An aluminum foil (A1085 in JIS) having a thickness of 30 μm wasarranged. An ion-permeable compound obtained by cross-linking a chitosanas polysaccharide with pyromellitic anhydride was arranged. Theion-permeable compound was 35000 in a number average molecular weight asmeasured by gel permeation chromatography (GPC). The ion-permeablecompound was 2.05×10⁻² S/cm in an ion permeability (σ₀=4.54×10⁻⁶ S/cm,σ₁=33.5×10⁻⁶S/cm, film thickness d=71 μm).

The ion-permeable compound, carbon fine particle a (acetylene black:average particle size 40 nm), and water in mass ratio of 40;40:20 weremixed and kneaded to obtain a paste.

The paste was applied to the aluminum foil by casting method with anapplicator (gap: 10 μm), was dried for 3 minutes in air at 180 ° C. toform a film a comprising the ion-permeable compound and the carbon fineparticle a on the aluminum foil, which allowed to obtain a collector foran electric double layer capacitor.

The film a after drying was 5 μm in a thickness, and content of carbonfine particle a in the film a was 60% by mass. When an electricconductivity was measured by a normal tester, enough electricconductivity was identified.

FIG. 1 is a schematic illustration of sectional formation of thecollector obtained by the above. As shown in FIG. 1, the collector foran electric double layer capacitor in the invention is that the film a(2) is laminated on the aluminum foil (1). Carbon fine particle (3) andion-permeable compound (4) are included in the film a (2).

Example 2

A paste comprising an activated carbon, carbon fine particle b, binderand solvent in accordance with the following recipe was applied to thecollector obtained by EXAMPLE 1 to form a polarizable electrode layer(film b) comprising the activated carbon as a main ingredient having athickness of 200 μm, which allowed to make an electrode for an electricdouble layer capacitor. Activated carbon: alkali activated carbon having85 parts by mass a specific surface area of 1500 m²/g Carbon fineparticle b: Acetylene Black (average  5 parts by mass particle size 40nm) Binder: polyvinylidene fluoride (PVDF) 10 parts by mass Solvent:N-methyl-2-pyrrolidone (NMP) 8.5 parts by mass  (10% by mass to theactivated carbon)

The electrode for an electric double layer capacitor was stamped intotwo discoidal electrodes having a diameter of 20 mm which were fittedinto a capacitor vessel for evaluation. The two electrodes were piled inthe state that a separator was interposed between the electrodes, andwere put in the capacitor vessel for evaluation. An organic electrolyticsolution was poured in the vessel to immerse the electrode et al.Finally, the vessel was covered to make an electric double layercapacitor for evaluation.

As the organic electrolytic solution, “LIPASTE-P/EAFIN” (1 mol/l) astrade name produced by TOMIYAMA PURE CHEMICAL INDUSTRIES LTD. comprisingpropylene carbonate as solvent and (C₂H₅)₄NBF₄ as electrolyte was used.

FIG. 2 is a schematic illustration of sectional formation of theelectrode obtained by the above. As shown in FIG. 2, the electrode foran electric double layer capacitor in the invention is that the film a(2) is laminated on the aluminum foil (1), and the film b (6) is furtherlaminated on the film a. Binder (7), activated carbon (5), and carbonfine particle b (3) are included in the film b (6).

An impedance and an electric capacity of the electric double layercapacitor obtained by the above were determined. The results are shownin Table 1.

Impedance was measured at 1 kHz with an impedance measure (PAN110-5AM)produced by KIKUSUI ELECTRONICS CORPORATION. Electric capacity wasmeasured by charge and discharge operations between 0 V and 2.5 V at1.59 mA/cm² in a current density with a charge-discharge unit(HJ-101SM6) produced by HOKUTO DENKO CORPORATION. An electric capacityper cell (F/coll) of the electric double layer capacitor was calculatedfrom discharge property curve in the 2nd constant current dischargeoperation.

A retention rate of the electric capacity was determined from theformula: (an electric capacity of the 20th cycle operation)/(an electriccapacity of the 20nd cycle operation)×100.

As shown in Table 1, an electric double layer capacitor obtained byusing the collector in the invention has low impedance, high electriccapacity per cell, and good retention rate.

Example 3

A collector for an electric double layer capacitor was obtained by thesame manner as EXAMPLE, 1 except that the carbon fine particle a(acetylene black) used in EXAMPLE 1 was replaced with a vapor growncarbon fiber (VGCF (Registered Trade Mark) produced by SHOWA DENKO K.K.,fiber length 20 μm). An electrode for an electric double layercapacitor, and an electric double layer capacitor were obtained by thesame manner as EXAMPLE 2 except that the collector was used. The resultsare shown in Table 1.

Example 4

An electrode for an electric double layer capacitor, and an electricdouble layer capacitor were obtained by the same manner as EXAMPLE 2except that the carbon fine particle b (acetylene black) used in EXAMPLE2 was replaced with a vapor grown carbon fiber (VGCF (Registered TradeMark) produced by SHOWA DENKO K.K., fiber length 20 μm). The results areshown in Table 1.

Example 5

An ion-permeable compound obtained by cross-linking a chitin aspolysaccharide with maleic anhydride was arranged. The ion-permeablecompound was 30000 in a number average molecular weight as measured byGPC. A paste was made by the same manner as EXAMPLE 1 except that theabove ion-permeable compound was used, which allowed to obtain acollector comprising a film comprising the ion-permeable compound andcarbon fine particle, and aluminum foil.

An electric double layer capacitor was obtained by the same manner asEXAMPLE 2 except that the collector was used. An electric capacity,retention rate, internal resistance, and impedance were similarlydetermined. The results are shown in Table 1.

Example 6

A paste was obtained by the same manner as EXAMPLE 1 except that analuminum foil (A1085) used in EXAMPLE 1 was replaced with an aluminumfoil (A3003), and ion-permeable compound was replaced with a compound(31000 in a number average molecular weight as measured by GPC) obtainedby cross-linking chitosan as polysaccharide with acrylonitrile, whichallowed to obtain a collector comprising a film comprising anion-permeable compound and a carbon fine particle, and an aluminum foil.

An electric double layer capacitor was obtained by the same manner asEXAMPLE 2 except that the collector was used. Electric capacity,retention rate, internal resistance, and impedance were similarlydetermined. The results are shown in Table 1.

Example 7

A paste was obtained by the same manner as EXAMPLE 1 except thation-permeable compound used in EXAMPLE 1 was replaced with a compound(22000 in a number average molecular weight as measured by GPC) obtainedby cross-linking chitosan as polysaccharide with trimellitic anhydride,which allowed to obtain a collector comprising a film comprising anion-permeable compound and a carbon fine particle, and an aluminum foil.

An electric double layer capacitor was obtained by the same manner asEXAMPLE 2 except that the collector was used.. Electric capacity,retention rate, internal resistance, and impedance were similarlydetermined. The results are shown in Table 2.

Example 8

An ion-permeable compound obtained by cross-linking a chitosan aspolysaccharide with acryloritrile was arranged. A film having athickness of 0.5 μm of the ion-permeable compound was evaluated by tapepeeling test. Any of 100 squares did not come off. The ion-permeablecompound was 26000 in a number average molecular weight as measured byGPC.

A paste was made by the same manner as EXAMPLE 1 except that the abovecompound obtained by cross-linking chitosan with acrylonitrile, and acompound obtained by cross-linking chitosan with trimellitic anhydride(22000 in number average molecular weight as measured by GPC) were usedtogether, which allowed to obtain a collector comprising a filmcomprising the ion-permeable compound and a carbon fine particle, and analuminum foil.

An electric double layer capacitor was obtained by the similar manner toEXAMPLE 2. An electric capacity, retention rate, internal resistance,and impedance were similarly determined. The results are shown in Table2.

Comparative Example 1

A collector for an electric double layer capacitor was obtained by thesame manner as EXAMPLE 1 except that the carbon fine particle a was notused, that is, a solution only comprising an ion-permeable compound andwater was used instead of the paste used in EXAMPLE 1. The results areshown in Table 2. When an electric conductivity was measured by a normaltester, electricity did not move.

Comparative Example 2

An electrode for an electric double layer capacitor, and an electricdouble layer capacitor were obtained by the same manner as EXAMPLE 2except that aluminum foil made from A1085 in which the surface of thefoil was etched was used instead of the collector used in EXAMPLE 2. Theresults are shown in Table 2.

Comparative Example 3

An electric double layer capacitor was made by the same manner asEXAMPLE 1 and EXAMPLE 2 except that the ion-permeable compound wasreplaced with PVDF. Ion permeability of PVDF was 0.81×10⁻² S/cm(σ₀=4.54×10⁻⁶ S/cm, σ₁=6.42×10⁻⁶ S/cm, film thickness d=433 μm).Retention rate and internal resistance were determined by the samecondition as EXAMPLE 2. The results are shown in Table 2. The surface ofthe collector widely peeled when the surface was rubbed with a clothpenetrated with propylene carbonate, though the electric double layercapacitor was able to be produced. Even though the electric double layercapacitor obtained in COMPARATIVE EXAMPLE 3 is good in initial property,it is supposed that the capacitor can not stand longtime run.

Comparative Example 4

An electric double layer capacitor was made by the same manner asEXAMPLE 1 and EXAMPLE 2 except that the ion-permeable compound wasreplaced with PVA (Polyvinyl alcohol) binder. Retention rate andinternal resistance were determined by the same condition as EXAMPLE 2.The results are shown in Table 2. The surface of the collector widelypeeled by a tape peeling test being the same as COMPARATIVE EXAMPLE 3,though the electric double layer capacitor was able to be produced. Eventhough the electric double layer capacitor obtained in COMPARATIVEEXAMPLE 4 is good in initial property, it is supposed that the capacitorcan not stand longtime run. TABLE 1 Film a Film b carbon ion- carbonTester electric retention fine permeable fine conductible impedancecapacity rate particle a compound particle b test (Ω) (F/cell) (%) Ex. 1Acetylene chitosan - — conductible — — — Black pyromellitic anhydrideEx. 2 Acetylene chitosan - Acetylene conductible 1.51 1.69 98 Blackpyromellitic Black anhydride Ex. 3 VGCF chitosan - Acetylene conductible1.54 1.20 98 pyromellitic Black anhydride Ex. 4 Acetylene chitosan -VGCF conductible 1.39 1.79 99 Black pyromellitic anhydride Ex. 5Acetylene chitin - Acetylene conductible 1.39 1.72 98 Black maleic Blackanhydride Ex. 6 Acetylene chitosan - Acetylene conductible 1.51 1.69 98Black acrylonitrile Black

TABLE 2 Film a Film b carbon ion- carbon Tester electric retention finepermeable fine conductible impedance capacity rate particle a compoundparticle b test (Ω) (F/cell) (%) Ex. 7 Acetylene chitosan - Acetyleneconductible 1.52 1.68 98 Black trimellitic Black anhydride Ex. 8Acetylene chitosan - Acetylene conductible 1.53 1.72 98 Blacktrimellitic Black anhydride + chitosan - acrylonitrile Comp. —chitosan - — isolation — — — Ex. 1 pyromellitic anhydride Comp. — —Acetylene conductible 4.32 1.22 97 Ex. 2 Black Comp Acetylene PVDFAcetylene conductible 17.0 1.65 80 Ex. 3 Black Black Comp Acetylene PVAAcetylene conductible 15.2 1.62 70 Ex. 4 Black Black

According to Table 1 and Table 2, it is known that any electric doublelayer capacitors (EXAMPLEs) using the collector for an electric doublelayer capacitor in the invention have lower impedance, higher electriccapacity, and more excellent retention rate than COMPARATIVE EXAMPLEs.The capacitor in the invention can be charged and discharged by largeelectric current (that is quick chargable/dischargable), and it isconsidered that the capacitor in the invention has greater performancethan the conventional electric double layer capacitor.

Though intimate ground that the electric double layer capacitor in theinvention has low impedance and high electric capacity isn't known, itis guessed that ion-permeable compound and conductive carbon fineparticle a in the film a help movement of ion and electron respectively,which results in making ion and electron smoothly move between apolarizable electrode layer (film b) and a conductive sheet (aluminumfoil).

1. A collector for an electric double layer capacitor comprising: aconductive sheet, and a film a comprising ion-permeable compound andcarbon fine particle a, in which the film a is on the conductive sheet.2. The collector for an electric double layer capacitor according toclaim 1, in which the conductive sheet is aluminum foil, etching-foil ofaluminum or punching-foil of aluminum.
 3. The collector for an electricdouble layer capacitor according to claim 1, in which the ion-permeablecompound is a compound not being swellable with an organic solvent. 4.The collector for an electric double layer capacitor according to claim1, in which the ion-permeable compound is a compound which does not comeoff in a friction peeling test with organic solvent.
 5. The collectorfor an electric double layer capacitor according to claim 1, in whichthe ion-permeable compound is 1×10² S/cm or more in a permeability offluoride ion.
 6. The collector for an electric double layer capacitoraccording to claim 1, in which the ion-permeable compound is 50,000 orless in an average molecular weight.
 7. The collector for an electricdouble layer capacitor according to claim 1, in which the ion-permeablecompound is polysaccharides or cross-linked polysaccharides.
 8. Thecollector for an electric double layer capacitor according to claim 1,in which the ion-permeable compound is polysaccharides cross-linked byany of acrylamide, acrylonitrile, chitosan pyrrolidone carboxylate,hydroxypropylchitosan, phthalic anhydride, maleic anhydride, trimelliticanhydride, pyromellitic anhydride, and acid anhydride.
 9. The collectorfor an electric double layer capacitor according to claim 7, in whichthe polysaccharides is chitosan or chitin.
 10. The collector for anelectric double layer capacitor according to claim 1, in which the filma does not come off in a tape peeling test (JIS D0202-1988).
 11. Thecollector for an electric double layer capacitor according to claim 1,in which the film a is obtained by heat-curing.
 12. The collector for anelectric double layer capacitor according to claim 1, in which the filmfurther comprises activated carbon a.
 13. The collector for an electricdouble layer capacitor according to claim 1, in which the carbon fineparticle a is acicular or cylindric shape.
 14. An electrode for anelectric double layer capacitor comprising: a collector for an electricdouble layer capacitor according to claim 1, and a film b comprising abinder, a carbon fine particle b, and an activated carbon b, in whichthe film b is on the film a in the collector.
 15. The electrode for anelectric double layer capacitor according to claim 14, in which thecarbon fine particle b is acicular or cylindric shape.
 16. The electrodefor an electric double layer capacitor according to claim 14, in whichthe activated carbon b is 800 to 2500 m^(2/)g in a BET specific surfacearea.
 17. The electrode for an electric double layer capacitor accordingto claim 14, in which the binder comprises an ion-permeable compound.18. A method of producing a collector for an electric double layercapacitor comprising steps of: coating a solution or dispersion of anion-permeable compound, a carbon fine particle a and a solvent on to aconductive sheet, and drying the coat to form a film a.
 19. The methodof producing a collector for an electric double layer capacitoraccording to claim 18, in which the ion-permeable compound is 1×10⁻²S/cmor more in a permeability of fluoride ion.
 20. The method of producing acollector for an electric double layer capacitor according to claim 18,in which the ion-permeable compound is 50,000 or less in an averagemolecular weight.
 21. The method of producing a collector for anelectric double layer capacitor according to claim 18, in which theion-permeable compound is polysaccharides or cross-linkedpolysaccharides.
 22. The method of producing a collector for an electricdouble layer capacitor according to claim 18, in which the ion-permeablecompound is polysaccharictes cross-linked by any of acrylamide,acrylonitrile, chitosan pyrrolidone carboxylate, hydroxypropylchitosan,phthalic anhydride, maleic anhydride, trimellitic anhydride,pyromellitic anhydride, and acid anhydride.
 23. The method of producinga collector for an electric double layer capacitor according to claim18, in which the carbon fine particle a is acicular or cylindric shape.24. The method of producing an electrode for an electric double layercapacitor comprising steps of: coating a solution or dispersion of abinder, a carbon fine particle b, an activated carbon b, and a solventon to the film a in the collector for an electric double layer capacitoraccording to claim 1, and drying the coat to form a film b.
 25. Themethod of producing an electrode for an electric double layer capacitorcomprising steps of: coating a solution or dispersion of anion-permeable compound, a carbon fine particle a and a solvent on to aconductive sheet, drying the coat to form a film a coating a solution ordispersion of a binder, a carbon fine particle b, an activated carbon b,and a solvent on to the film a, and drying the coat to form a film b.26. The method of producing an electrode for an electric double layercapacitor according to claim 25, in which the ion-permeable compound is1×10⁻²S/cm or more in a permeability of fluoride ion.
 27. The method ofproducing an electrode for an electric double layer capacitor accordingto claim 25, in which the ion-permeable compound is 50,000 or less in anaverage molecular weight.
 28. The method of producing an electrode foran electric double layer capacitor according to claim 25, in which theion-permeable compound is polysaccharides or cross-linkedpolysaccharides.
 29. The method of producing an electrode for anelectric double layer capacitor according to claim 25, in which theion-permeable compound is polysaccharides cross-linked by any ofacrylamide, acrylonitrile, chitosan pyrrolidone carboxylate,hydroxypropylchitosan, phthalic anhydride, maleic anhydride, trimelliticanhydride, pyromellitic anhydride, and acid anhydride.
 30. The method ofproducing an electrode for an electric double layer capacitor accordingto claim 25, in which the carbon fine particle a is acicular orcylindric shape.
 31. The method of producing an electrode for anelectric double layer capacitor according to claim 24, in which thecarbon fine particle b is acicular or cylindric shape.
 32. The method ofproducing an electrode for an electric double layer capacitor accordingto claim 24, in which the activated carbon b is 800 to 2500 m²/g in aBET specific surface area.
 33. An electric double layer capacitorcomprising: electrode for an electric double layer capacitor accordingto claim 14, separator, and an electrolytic solution.
 34. The electricdouble layer capacitor according to claim 33 which is laminate typecapacitor or reel type capacitor.
 35. A method of producing an electricdouble layer capacitor comprising steps of: piling the electrode for anelectric double layer capacitor according to claim 14 and separator, andimmersing the pile of the electrode and the separator in an electrolyticsolution.
 36. A power supply system comprising the electric double layercapacitor according to claim
 33. 37. A vehicle in which the electricdouble layer capacitor according to claim 33 is employed.
 38. A railroadin which the electric double layer capacitor according to claim 33 isemployed.
 39. A ship in which the electric double layer capacitoraccording to claim 33 is employed.
 40. An aircraft in which the electricdouble layer capacitor according to claim 33 is employed.
 41. A portableapparatus in which the electric double layer capacitor according toclaim 33 is employed.
 42. An apparatus for office work in which theelectric double layer capacitor according to claim 33 is employed.
 43. Asolar power generation system in which the electric double layercapacitor according to claim 33 is employed.
 44. A wind power generationsystem in which the electric double layer capacitor according to claim33 is employed.
 45. A communication apparatus in which the electricdouble layer capacitor according to claim 33 is employed.
 46. Anelectronic tag in which the electric double layer capacitor according toclaim 33 is employed.